CN101264453A - Titanium-silicon molecular sieve/tripolite composite catalyst and preparation - Google Patents
Titanium-silicon molecular sieve/tripolite composite catalyst and preparation Download PDFInfo
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- CN101264453A CN101264453A CNA2008100344314A CN200810034431A CN101264453A CN 101264453 A CN101264453 A CN 101264453A CN A2008100344314 A CNA2008100344314 A CN A2008100344314A CN 200810034431 A CN200810034431 A CN 200810034431A CN 101264453 A CN101264453 A CN 101264453A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a Ti-Si molecular sieve/diatomite composite catalyst and a preparation method thereof, which is characterized in that: the catalyst is formed by compounding Ti-Si molecular sieve (such as TS-1 and TS-2) and diatomite with particular chemical property which is treated in a particular way, and is modified chemically by transition metal oxide after molding; the preparation method comprises the following steps: (1) after being treated with acid solution and alkaline solution, the diatomite needs heat treatment in high temperature to obtain particular chemical property; (2) the molding Ti-Si molecular sieve/diatomite composite catalyst is modified chemically by transition metal oxide (such as lanthanum and nickel). The composite catalyst can be used as the catalyst of selective oxidation reaction of the organic compound (such as the catalytic hydroxylation reaction of phenol) on fixed bed liquidoid, which uses hydrogen peroxide as the oxidant. The Ti-Si molecular sieve/diatomite composite catalyst has the advantages of high catalytic activity, high stability, long service life and easy separation, recovery and regeneration of the catalyst. When using the catalyst in the hydroxylation reaction of phenol of fixed bed liquidoid, under the reaction conditions of 84 DEG C, atmospheric pressure and 8.46h<-1> space velocity, the conversion rate of phenol is greater than 33%, the selectivity of diphenol reaches 99.9%, and the effective use rate of hydrogen peroxide is greater than 85%.
Description
The present invention relates to a kind of preparation method of load type titanium silicalite molecular sieve, more particularly relate to a kind of preparation method of titanium-silicon molecular sieve/tripolite composite catalyst, it is the selective oxidation reaction of fixed bed liquid phase organic compound of oxidant that this catalyst can be used for the hydrogen peroxide, catalytic hydroxylation reaction as phenol, not only has advantages of high catalytic activity, and have advantages of higher stability and long service life, catalyst is easy to separate, reclaims and regeneration.
Background technology
Since the seventies, the ZSM-5 zeolite molecular sieve came out, contain hetero-atom molecular-sieves such as Cr, Ti, Zr, Be, P, V and be synthesized success in succession, the research development in recent years of zeolite molecular sieve that wherein contains Ti is very fast.Since adopting TPAOH (TPAOH), people such as nineteen eighty-three Taramasso are the template agent, tetraethyl titanate is the titanium source, synthetic titanium-silicon molecular sieve TS-1 (patent GB 2071071A, the USP4 of success with MFI structure, 410,501) after, have the TS-2 of MEL structure and have Ti-MCM-48 than macroporous structure etc. also constantly to be successfully synthesized.
The maximum characteristics of HTS are can highly selective shape selective catalysis oxidation of organic compounds in the presence of the low concentration hydrogen peroxide, reaction process is simple simultaneously, oxidant is cheap low concentration hydrogen peroxide, its catabolite is the oxygen G﹠W, can not cause any pollution, belong to environmental type catalytic reaction technology environment.At present, be that the HTS of representative has been widely used in reactions such as benzene or phenol hydroxylation, cyclohexanone oxamidinating, alkene epoxidation, oxidation of alcohols, partial oxidation of alkanes with TS-1.But HTS synthesizes cost costliness, synthesis condition harshness, the general particle diameter of the former powder of He Cheng Ti-Si zeolite less (0.2-0.5 μ m) in addition, in course of reaction, be easy to be carried secretly by liquid stream, be difficult for after reaction finishes and liquid phase separation, recovery, can not in fixed-bed catalytic reactor, use.Because the running cost height has hindered the extensive use of HTS in chemical industry.
For overcoming the above problems, patent (WO 9412277, and US 5736479) with particle diameter less than the activated carbon of 32 μ m or oxide (as SiO
2, TiO
2, Al
2O
3Deng) be carrier, before the molecular sieve crystallization, join in the synthesis mother liquid of HTS, by the growth of TS-1 on carrier, made the TS-1 of support type, with the ammoxidation of cyclohexanone, the reactions such as oxidation of hexane, obtained certain effect.
It is in 30% the Ludox that United States Patent (USP) (US 4701428) joins concentration with the unfired TS-1 that obtains after the crystallization, after the spray-dried then and roasting, obtains the TS-1/SiO that particle diameter is 20 μ m
2Microballoon.
Chinese patent (CN 1554483A) proposes to add the graphite powder of inertia in HTS hydro-thermal synthetic system, can make the HTS of support type, and use it for the oximation reaction of cyclohexanone, the conversion ratio of cyclohexanone and the selectivity of cyclohexanone oxime all can reach more than 95%.
Japan Patent (JP 8103659) has prepared thin layer catalyst by be coated with the last layer molecular sieve on the surface of silicon bead, makes active component in the carrier surface enrichment, can utilize molecular sieve component to greatest extent.
After the HTS loadization, can effectively utilize molecular sieve component on the one hand, obtain catalytic activity preferably; Can reduce the use cost of HTS on the other hand, the large-scale industrial that promotes HTS is used.
Summary of the invention
The purpose of this invention is to provide a kind of by HTS with have the compound Preparation of catalysts technology of diatomite of chemical characteristic, can be used for selective oxidation reactions such as catalysis of phenol hydroxylating, alkene epoxidation.Conventional HTS particle is little, use cost is high with separate difficult problem in industrial applications to overcome, and also can obviously improve reactant and the diffusion of product in the catalyst duct simultaneously, improves reaction rate and product selectivity.
Catalyst of the present invention is by HTS and have compound the forming of diatomite of particular characteristic, and it is carried out chemical modification handle, and wherein diatomite accounts for 10～80% of total catalyst weight.
The chemical formula of said HTS is: xTiO
2. (1-x) SiO
2, wherein x is with molar ratio computing, x=Ti/ (Ti+Si), the span 0.003～0.1 of x;
Said HTS is TS-1 and TS-2, wherein preferred TS-1;
Said diatomite with particular characteristic is meant the diatomite with particular chemical performance through specially treated.The method of handling is, handles the back with acid solution and handles with aqueous slkali, spends deionised water then to neutral, and roasting is carried out in the oven dry back in air.
Said diatomaceous treatment step is as follows:
5～20g diatomite is placed the 100mL conical flask, with 6～70% inorganic acids of 10～80mL (as sulfuric acid, nitric acid, hydrochloric acid, wherein be preferably sulfuric acid) mix with diatomite, bottleneck assembling reflux, be heated to backflow, keep being cooled to room temperature behind temperature backflow 1.5～12h, with a certain amount of aqueous slkali (as NaOH, potassium hydroxide etc., wherein being preferably sodium hydroxide solution) titration to pH value is 9～12, be warmed up to 50～100 ℃ of heating 0.5～2h again, be preferably 85～95 ℃ of insulation 0.5～1h.Spend deionised water then to neutral, use 20～250mL absolute ethanol washing again, filter, filter cake is in 80～150 ℃ baking oven behind dry 6～18h, in the mode of temperature programming, be warming up to 300 ℃～1200 ℃ from room temperature gradually with 1～14h, and under this temperature, keep 1～24h.
Titanium-silicon molecular sieve/tripolite Preparation of catalysts method of the present invention comprises the steps: with 0.1～4g: diatomite and the HTS mechanical mixture of 1g ratio after with roasting is even, compressing tablet, is crushed to 10～80 orders, preferred 20～40 orders.
For improving activity of such catalysts and selectivity, molecular sieve/tripolite catalyst of the present invention also will adopt the aqueous solution of slaine or mixed metal salt that it is carried out modification and handle.Said slaine can be nitrate, acetate, ammonium salt etc., as cerous nitrate, ferric nitrate, cobalt nitrate, copper nitrate, lanthanum nitrate, nickel nitrate, manganese acetate, zirconium nitrate, ammonium metavanadate, ammonium tungstate, ammonium molybdate etc., and wherein preferred lanthanum nitrate and nickel nitrate.When modification is handled, titanium-silicon molecular sieve/tripolite: water: slaine=1g: 0.5～40mL: 0.01～5g, preferred range is 1g: 1～20mL: 0.01～1g.
The step of catalyst being carried out modification is as follows:
Slaine or mixed metal salt are dissolved in 1～20mL deionized water, 1g titanium-silicon molecular sieve/tripolite particle are immersed wherein dip time 2～10h.In 80～150 ℃ behind dry 4～16h, mode with temperature programming is carried out roasting, rise to 300～900 ℃ from room temperature with 1～14h, under this temperature, keep 1～24h then, preferably rise to 300～800 ℃ of roasting 2～10h, obtain the titanium-silicon molecular sieve/tripolite catalyst of metal oxide modified with 1～6h.The load capacity of metal oxide is 0.01～15% (quality percentage composition).
It is the liquid phase selective catalytic oxidation reaction of organic compound of oxidant that catalyst of the present invention can be used for the hydrogen peroxide, the fixed bed catalyst process that is suitable for continous way is as reactions such as benzene or phenol hydroxylation, cyclohexanone oxamidinating, alkene epoxidation, oxidation of alcohols, partial oxidation of alkanes.Catalyst of the present invention is particularly useful for the continous way fixed bed catalyst process of one step of phenol catalytic hydroxylation preparing benzenediol.
The investigation process of Pyrogentisinic Acid's one step catalytic hydroxylation preparing benzenediol catalytic activity is: the employing caliber is 15 millimeters continous way fixed bed reactors, and catalyst places the reactor constant temperature zone.After reactor is preheated to required temperature, with phenol, H
2O
2Reach solvent mixture by the bottom input reactor of measuring pump from reactor, product is from the reactor head diffluence, and with the composition and the concentration of gas chromatograph analytical reactions liquid, analysis result adopts the corrected area normalization method to calculate the H in raw material and the product
2O
2Concentration adopts iodometric determination.
Catalyst form of the present invention can be particle, extrudate or formed body, and the particle diameter of catalyst and shape can design according to the needs of industrial reaction.Catalyst of the present invention has overcome the separation problem of conventional powder shape Ti-Si catalyst.The diatomite that uses in catalyst of the present invention is through special chemistry and heat treated, removed the iron oxide in easy formation acid site, impurity such as aluminium oxide, simultaneously by having formed the passivation on a large amount of central hole structures and surface after the high-temperature process, thereby the mass transfer that helps reactant and product in the oxidation reaction such as phenol one step hydrogen peroxide hydroxylating, the utilization rate and the product selectivity of hydrogen peroxide have been improved, owing to adopted with diatomaceous compound, therefore obviously reduced the use amount of HTS, both reduce the use cost of catalyst, also overcome the difficult difficulty of separating of titanium-silicon molecular sieve catalyst simultaneously.
Catalyst of the present invention is the catalyst through metal oxide modified, so catalytic performance is significantly improved again, is used for the phenol-hydrogen peroxide hydroxylating, can make the selectivity and the H of benzenediol
2O
2The obvious raising of effective rate of utilization.
Use the selective oxidation process of catalyst organic compound of the present invention, can under the atmospheric low-temperature degree, carry out, the reaction condition gentleness, operation is easy to control.
The invention will be further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
10g diatomite is placed the 100mL conical flask, add 100mL40% sulfuric acid, bottleneck assembling reflux is heated to 80 ℃ in water-bath, be cooled to room temperature behind the insulation 4h, is 10 with 20% sodium hydroxide solution titration to pH value.Continue to heat to 90 ℃, be cooled to room temperature behind the insulation 0.5h, spend deionised water to neutral, use the 100mL absolute ethanol washing again, filter, filter cake is in 110 ℃ baking oven behind the dry 14h, heating rate with 250 ℃/h rises to 1000 ℃ from room temperature, and keeps 4h under this temperature.
The diatomite that 3.6g TS-1 and 5.4g were handled mixes, and compression molding is crushed to 20～40 orders.Phenol hydroxylation is reflected in the fixed bed glass reactor that internal diameter is 15mm and carries out, and catalyst amount 7g places the reactor constant temperature zone, and two ends are sealed with broken ceramics, after reactor is preheated to 84 ℃ of required reaction temperatures, with phenol, H
2O
2(30%) and acetone (phenol and acetone mass ratio are 1.25: 1, phenol and H
2O
2Mol ratio is 3: 1) mixture is by the bottom input reactor of measuring pump by reactor, and the reaction mass air speed is 8.46h
-1Pick up counting sample analysis behind the stable reaction 1h from the outflow of first drop of liquid.Reaction evaluating the results are shown in Table 1.
[embodiment 2]
With the difference of embodiment 1 be: diatomite extends to 12h 1000 ℃ roasting time, and other conditions are identical with embodiment 1.The evaluating catalyst condition is seen example 1, and reaction evaluating the results are shown in Table 1.
[embodiment 3]
With the difference of embodiment 1 be: without the heat treatment of roasting, other conditions are identical with embodiment 1 after the diatomite drying after the process chemical treatment.The evaluating catalyst condition is seen example 1, and reaction evaluating the results are shown in Table 1.
[embodiment 4]
With the difference of embodiment 1 be: only contain 9g TS-1 in the catalyst, do not contain diatomite, other conditions are identical with embodiment 1.The evaluating catalyst condition is seen example 1, and reaction evaluating the results are shown in Table 1.
[embodiment 5]
With the difference of embodiment 1 be: TS-1 is changed to TS-2, and other conditions are identical with embodiment 1.The evaluating catalyst condition is seen example 1, and reaction evaluating the results are shown in Table 1.
The result of the phenol catalytic hydroxylation reaction of table 1. embodiment 1～5
[embodiment 6]
With 0.1063g La (NO
3)
3.6H
2O is dissolved in the 20mL deionized water and makes maceration extract.The catalyst 8g that gets embodiment 1 preparation puts into 110 ℃ the dry 16h of baking oven after impregnated in and wherein leaving standstill 6h, and the catalyst that drying is good is in the mode of temperature programming, rise to 550 ℃ from room temperature with 3h after roasting 6h, make La
2O
3The titanium-silicon molecular sieve/tripolite catalyst of modification, wherein La
2O
3Account for 0.5% (quality percentage composition) of catalyst quality.The evaluating catalyst condition is seen example 1, and reaction evaluating the results are shown in Table 2.
[embodiment 7]
With the difference of embodiment 6 be: with 0.4252g La (NO
3)
3.6H
2O is dissolved in the 20mL deionized water and makes maceration extract, and other conditions are identical with embodiment 6.The La that is making
2O
3In the titanium-silicon molecular sieve/tripolite catalyst of modification, La
2O
3Account for 2% of catalyst quality.The evaluating catalyst condition is seen example 1, and reaction evaluating the results are shown in Table 2.
[embodiment 8]
With the difference of embodiment 6 be: with 0.8508g La (NO
3)
3.6H
2O is dissolved in the 20mL deionized water and makes maceration extract, and other conditions are identical with embodiment 6.The La that is making
2O
3In the titanium-silicon molecular sieve/tripolite catalyst of modification, La
2O
3Account for 4% of catalyst quality.The evaluating catalyst condition is seen example 1, and reaction evaluating the results are shown in Table 2.
[embodiment 9]
With the difference of embodiment 6 be: with 1.063g La (NO
3)
3.6H
2O is dissolved in the 20mL deionized water and makes maceration extract, and other conditions are identical with embodiment 6.The La that is making
2O
3In the titanium-silicon molecular sieve/tripolite catalyst of modification, La
2O
3Account for 5% of catalyst quality.The evaluating catalyst condition is seen example 1, and reaction evaluating the results are shown in Table 2.
[embodiment 10]
With the difference of embodiment 6 be: with 1.276g La (NO
3)
3.6H
2O is dissolved in the 20mL deionized water and makes maceration extract, and other conditions are identical with embodiment 6.The La that is making
2O
3In the titanium-silicon molecular sieve/tripolite catalyst of modification, La
2O
3Account for 6% of catalyst quality.The evaluating catalyst condition is seen example 1, and reaction evaluating the results are shown in Table 2.
[embodiment 11]
With the difference of embodiment 6 be: with 0.1557g Ni (NO
3)
2.6H
2O is dissolved in the 20mL deionized water and makes maceration extract, and other conditions are identical with embodiment 6.In the titanium-silicon molecular sieve/tripolite catalyst of the NiO modification that makes, NiO accounts for 0.5% (quality percentage composition) of catalyst quality.The evaluating catalyst condition is seen example 1, and reaction evaluating the results are shown in Table 2.
[embodiment 12]
With the difference of embodiment 6 be: with 0.3114g Ni (NO
3)
2.6H
2O is dissolved in the 20mL deionized water and makes maceration extract, and other conditions are identical with embodiment 6.In the titanium-silicon molecular sieve/tripolite catalyst of the NiO modification that makes, NiO accounts for 1% (quality percentage composition) of catalyst quality.The evaluating catalyst condition is seen example 1, and reaction evaluating the results are shown in Table 2.
The result of the phenol catalytic hydroxylation reaction of table 2. embodiment 6～12
Claims (10)
1. the preparation method of a titanium-silicon molecular sieve/tripolite composite catalyst is characterized in that catalyst of the present invention by HTS and compound the forming of diatomite with particular characteristic, and it is carried out the chemical modification processing, and it consists of:
The weight percentage of HTS is 20～90%;
Diatomaceous weight percentage is 10～80%;
The metal oxide weight percentage is 0.1～10%.
2. HTS according to claim 1 is characterized in that being HTSs such as TS-1 or TS-2, and their chemical formula is: xTiO
2. (1-x) SiO
2, wherein x is with molar ratio computing, x=Ti/ (Ti+Si), the span 0.003～0.1 of x.
3. the diatomite with particular characteristic according to claim 1 is characterized in that referring to use the diatomite of handling with specific process with particular chemical performance.The method of its processing is, handles the back with acid solution and handles with aqueous slkali, spends deionised water then to neutral, and high-temperature roasting is carried out in the oven dry back in air.
4. diatomaceous processing method according to claim 3 is characterized in that comprising chemical treatment and high-temperature heat treatment, specifically comprises the steps:
Diatomite carries out acid treatment with inorganic acid solution (as sulfuric acid, nitric acid, hydrochloric acid, wherein being preferably sulfuric acid) under the condition that refluxes in having the device of backflow; At room temperature using aqueous slkali (as NaOH, potassium hydroxide etc., wherein being preferably NaOH) titration to pH value is 9～14, is preferably pH=9～10, is warmed up to 50～100 ℃ of insulation 0.5～2h again, is preferably 85～95 ℃ of insulation 0.5～1h; Spend deionised water then to neutral; Use absolute ethanol washing again, filter; Behind the filtration cakes torrefaction, under air and high temperature, carry out roasting.
5. diatomaceous high-temperature heat treatment according to claim 4, it is characterized in that in air, program to be warming up to 300～1200 ℃ of following roasting 4～24h through the diatomite after the chemical method processing, preferred sintering temperature is 800～1200 ℃, and roasting time is 10～24h.
6. the preparation method of titanium-silicon molecular sieve/tripolite composite catalyst according to claim 1 is characterized in that comprising the steps:
Diatomite and HTS after handling are mixed in proportion, carry out processing and forming, the particle diameter of catalyst and shape can design according to the needs of industrial reaction.In forming process, can also add 0～20% adhesive, all can not selected for use with the adhesive that reactant and product react under reaction condition.Preferred compression molding.
7. the preparation method of titanium-silicon molecular sieve/tripolite composite catalyst according to claim 1 is characterized in that carry out chemical modification with the aqueous solution of slaine or mixed metal salt to it to HTS and the compound catalyst that forms of diatomite with particular characteristic handles.Said slaine can be nitrate, acetate, ammonium salt etc., as cerous nitrate, ferric nitrate, cobalt nitrate, copper nitrate, lanthanum nitrate, nickel nitrate, manganese acetate, zirconium nitrate, ammonium metavanadate, ammonium tungstate, ammonium molybdate etc., and wherein preferred lanthanum nitrate and nickel nitrate.
8. the chemical modification method to titanium-silicon molecular sieve/tripolite composite catalyst according to claim 7 is characterized in that comprising the steps:
Slaine or mixed metal salt are dissolved in the deionized water, the titanium-silicon molecular sieve/tripolite catalyst granules is immersed wherein, dip time 2～10h, roasting is carried out in the mode of temperature programming in dry back, rise to 300～900 ℃ from room temperature with 1～14h, under this temperature, keep 1～24h (preferably to rise to 300～800 ℃ of roastings 2～10h), obtain the titanium-silicon molecular sieve/tripolite composite catalyst of metal oxide modified then with 1～6h.The load capacity of metal oxide is 0.01～15% (quality percentage composition).
9. titanium-silicon molecular sieve/tripolite composite catalyst according to claim 1, it is characterized in that can being used for the hydrogen peroxide is the liquid phase selective catalytic oxidation reaction of the organic compound of oxidant, as benzene or phenol hydroxylation, cyclohexanone oxamidinating, alkene epoxidation, oxidation of alcohols, partial oxidation of alkanes etc.Catalyst of the present invention is particularly useful for the continous way fixed bed catalyst process of one step of phenol catalytic hydroxylation preparing benzenediol.
10. the selective oxidation reaction of the organic compound of titanium-silicon molecular sieve/tripolite composite catalyst catalysis according to claim 9 is characterized in that using the fixed bed reactors system of continous way, is reflected in the liquid-solid two-phase and carries out.
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| CN102757406B (en) * | 2011-04-26 | 2014-04-16 | 中国石油化工股份有限公司 | Styrene epoxidation method for preparing styrene oxide |
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